Evan Lambertson, Dayana Bashirova, Kye E Hunter, Benhardt Hansen, Tim J Zuehlsdorff
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Computing linear optical spectra in the presence of nonadiabatic effects on graphics processing units using molecular dynamics and tensor-network approaches.
We compare two recently developed strategies, implemented in open source software packages, for computing linear optical spectra in condensed phase environments in the presence of nonadiabatic effects. Both approaches rely on computing excitation energy and transition dipole fluctuations along molecular dynamics (MD) trajectories, treating molecular and environmental degrees of freedom on the same footing. Spectra are then generated in two ways: in the recently developed Gaussian non-Condon theory, the linear response functions are computed in terms of independent adiabatic excited states, with non-Condon effects described through spectral densities of transition dipole fluctuations. For strongly coupled excited states, we instead parameterize a linear vibronic coupling Hamiltonian directly from spectral densities of energy fluctuations and diabatic couplings computed along the MD trajectory. The optical spectrum is then calculated using powerful, numerically exact tensor-network approaches. Both the electronic structure calculations to sample system fluctuations and the quantum dynamics simulations using tensor-network methods are carried out on graphics processing units, enabling rapid calculations on complex condensed phase systems. We assess the performance of the approaches using model systems in the presence of a conical intersection and the pyrazine molecule in different solvent environments.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
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